Certain substituted bis(2-benzoyl-3-oxo-cyclohexenyl)diamines

ABSTRACT

An herbicide compound of the formula ##STR1## wherein R is halogen, C 1  -C 2  alkyl, C 1  -C 2  alkoxy, nitro; cyano; C 1  -C 2  haloalkyl, or R a  SO n  -- wherein n is 0 or 2 and R a  is C 1  -C 2  alkyl; 
     R 1  is hydrogen or C 1  -C 4  alkyl; 
     R 2  is hydrogen or C 1  -C 4  alkyl; or 
     R 1  and R 2  together are alkylene having 2 to 5 carbon atoms; 
     R 3  is hydrogen or C 1  -C 4  alkyl; 
     R 4  is hydrogen or C 1  -C 4  alkyl; or 
     R 3  and R 4  together are oxo; 
     R 5  is hydrogen or C 1  -C 4  alkyl; 
     R 6  is hydrogen or C 1  -C 4  alkyl; or 
     R 5  and R 6  together are alkylene having 2 to 5 carbon atoms; 
     R 7  and R 8  independently are (1) hydrogen; (2) halogen; (3) C 1  -C 4  alkyl; (4) C 1  -C 4  alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1  -C 4  haloalkyl; (9) R b  SO n  -- wherein n is the integer 0, 1 or 2; and R b  is (a) C 1  -C 4  alkyl; (b) C 1  -C 4  alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR c  R d  wherein R c  and R d  independently are hydrogen or C 1  -C 4  alkyl; (11) R e  C(O)-- wherein R e  is C 1  -C 4  alkyl or C 1  -C 4  alkoxy; (12) SO 2  NR c  R d  wherein R c  and R d  are as defined; (13) --N(R c )C(O)R d  wherein R c  and R d  are as defined; or (14) --CH 2  CH 2  OCH 3  or --CH 2  CH 2  OC 2  H 5  ; with the proviso that R 7  is not at the 6-position; and 
     R 9  is hydrogen or C 1  -C 4  alkyl; and 
     R 10  is C 2  -C 6  alkylene, C 4  -C 8  alkenylene or C 4  -C 8  alkynylene.

BACKGROUND OF THE INVENTION

Herbicidal compounds having the structural formula ##STR2## wherein Rthrough R⁹ are as defined below and R¹⁰ is (a) hydrogen, (b) C₁ -C₆alkyl, (c) C₄ -C₆ cycloalkyl, (d) substituted C₁ -C₆ alkyl, (e) phenyl,(f) substituted phenyl, (g) C₁ -C₆ alkoxy, (h) benzyl, (i) phenethyl,(j) C₁ -C₄ alkyl--C(O)--, (k) C₁ -C₄ alkyoxy--C(O)--, (l) C₂ -C₆alkenyl, or (m) C₂ -C₆ alkynyl; are described in U.S. Pat. No. 4,775,411which is incorporated herein by reference.

DESCRIPTION OF THE INVENTION

This invention relates to certain substitutedbis(2-benzoyl-3-oxo-cyclohexenyl)diamines and their use as herbicides.

One embodiment of this invention is an herbicidal composition comprisingan herbicidally active substitutedbis(2-benzoyl-3-oxo-cyclohexenyl)diamines and an inert carrier thereforwherein the 2-position of each benzoyl moiety is substituted as hereinrecited and the 4-position preferably is substituted with an electronwithdrawing group such as halogen, cyano, trifluoromethyl or nitro. The4-, 5- and 6-positions of each cyclohex-2-enone moiety can besubstituted, preferably with the groups hereinafter recited. Morepreferably, the cyclohex-2-enone moieties have no substitution or the 4-or 6-positions are substituted with one or two methyl groups. The 3-, 4-and 5-positions of the benzoyl moieties can be substituted, preferablywith the groups hereinafter recited.

Also embodied within the scope of this invention are novel compoundshaving the following structural formula ##STR3##

R is halogen; C₁ -C₂ alkyl, preferably methyl; C₁ -C₂ alkoxy, preferablymethoxy; nitro; cyano; C₁ -C₂ haloalkyl, preferably trifluoromethyl; orR^(a) SO_(n) --wherein n is 0 or 2, preferably 2 and R^(a) is C₁ -C₂alkyl, preferably methyl. Preferably, R is chlorine, bromine, C₁ -C₂alkyl, C₁ -C₂ alkoxy, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethylor methylsulfonyl;

R¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl, most preferably R¹ is hydrogen or methyl;

R² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl, most preferably R² is hydrogen or methyl; or

R¹ and R² together are alkylene having 2 to 5 carbon atoms;

R³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl, most preferably R³ is hydrogen or methyl;

R⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl, most preferably R⁴ is hydrogen or methyl; or

R³ and R⁴ together are oxo;

R⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl, most preferably R⁵ is hydrogen or methyl;

R⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl, most preferably R⁶ is hydrogen; or

R⁵ and R⁶ together are alkylene having 2 to 5 carbon atoms;

R⁷ and R⁸ independently are (1) hydrogen; (2) halogen, preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4)C₁ -C₄ alkoxy, preferably methoxy or ethoxy; (5) trifluoromethoxy; (6)cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl;(9) R^(b) SO_(n) --wherein n is the integer 0, 1 or 2, preferably 0 or2; and R^(b) is (a) C₁ -C₄ alkyl, preferably methyl; (b) C₁ -C₄ alkylsubstituted with halogen, preferably chloromethyl, or trifluoromethyl;(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogenor C₁ -C₄ alkyl; (11) R^(e) C(O)--wherein R^(e) is C₁ -C₄ alkyl or C₁-C₄ alkoxy; (12) --SO₂ NR^(c) R^(d) wherein R.sup. c and R^(d) are asdefined; (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are asdefined; and (14) --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ ; with the provisothat R⁷ is not in the 6-position; and

R⁹ is hydrogen or C₁ -C₄ alkyl, preferably methyl or ethyl;

R₁₀ is C₂ -C₆ alkylene, preferably C₂ -C₄ alkylene, more preferablyethylene; C₄ -C₈ alkenylene or C₄ -C₈ alkynylene, preferably2-butenylene.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includeschlorine, bromine, iodine and fluorine. The term "C₁ -C₄ alkoxy"includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,isobutoxy and t-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkylgroups defined above under C₁ -C₄ alkyl in which one or more hydrogen isreplaced by chloro, bromo, iodo or fluoro.

The term "C₂ -C₆ alkylene" includes ethylene, propylene, and butylenewhere one or more hydrogen atoms optionally can be replaced with loweran alkyl group. The term "C₄ -C₈ alkenylene" includes 2-butenylene(--CH₂ --CH═CH--CH₂ --) and 2-pentenylene (--CH₂ --CH═CH--CH₂ --CH₂ --).The term "C₄ -C₈ alkynylene" includes 2-butynylene (--CH₂ --C.tbd.C--CH₂--).

Preferably, R is chlorine, bromine, nitro, methyl or trifluoromethyl,preferably R⁷ is in the 3-position. More preferably R⁷ is hydrogen, C₁-C₄ alkoxy, --CH₂ CH₂ OCH₃, --CH₂ CH₂ OC₂ H₅, or C₁ -C₄ thioalkyl. Morepreferably, R⁷ is hydrogen, methylthio, methoxy, ethoxy, --CH₂ CH₂ OCH₃or --CH₂ CH₂ OC₂ H₅. Most preferably, R⁸ is halogen, trifluoromethyl, orR^(b) SO_(n) wherein R^(b) is C₁ -C₄ alkyl, preferably methyl or ethyl,and n is the integer 0 or 2.

The compounds of this invention are active herbicides of a general type.That is, they are herbicidally effective against a wide range of plantspecies. The method of controlling undesirable vegetation of the presentinvention comprises applying an herbicidally effective amount of theabove-described compounds to the area where control is desired.

The compounds of the present invention can be prepared by the followingtwo-step general method. ##STR4## wherein R through R⁸ are as defined.

Generally, in step (a) the benzoyl dione is dissolved in an inertsolvent such as methylene dichloride and an excess, usually 150 to 200mole percent, of oxalyl chloride is added followed by a catalytic amount(0.1 equivalent) of dimethylformamide. The reaction mixture is stirredfrom one hour to one day at room temperature. The reaction product isisolated using conventional techniques. ##STR5## wherein R through R¹⁰are as defined.

Generally, in step (b) 2 mole of the 3-chloro-2-benzoylcycloalk-2-enoneare reacted with a mole of the diamine and a mole of a non-nucleophilicbase such as triethylamine in an inert solvent. The mixture is stirred 1to 18 hours and the desired product is isolated using conventionaltechniques.

The following examples teach the synthesis of a representative compoundof this invention.

EXAMPLE I 3-Chloro-2-(2-chloro-4-methanesulfonylbenzoyl)cyclohex-2-enone ##STR6##

2-(2-Chloro-4-methanesulfonylbenzoyl)-cyclohexane -1,3-dione [9.8 grams(g.), 30 millimole (mmol)] was dissolved in 100 milliliters (ml)methylene chloride and stirred at room temperature. To this solution wasadded oxalyl chloride (5.7 g., 45 mmol) followed by dimethylformamide(0.5 ml) in portions small enough to control effervescence. Theresulting solution was stirred for 4 hours and then poured into waterand extracted with methylene chloride. The organic layer was washedagain with water, saturated K₂ CO₃ solution and then dried with MgSO₄and the solvent evaporated to yield3-chloro-2(2-chloro-4-methanesulfonylbenzoyl) cyclohex-2-enone (7.3 g.,70%) as an oil which was used without further purification.

EXAMPLE II N,N'-dimethyl-N,N'-di(2-(2-chloro-4-methanesulfonylbenzoyl)-3-oxo-cyclohexenvl)ethylenediamine ##STR7##

3-Chloro-2-(2-chloro-4-methanesulfonylbenzoyl) -cyclohex-2-enone (1.8g., 5 millimole) was dissolved in 50 ml of methylene chloride andstirred at room temperature. A mixture of N,N'-dimethylethylene diamine(0.22 g., 2.5 mmol mole) and triethylamine (0.5 g., 5 mml) in 10 ml ofmethylene chloride was added dropwise over 20 minutes and the resultingsolution was stirred for 2 hours. The reaction mixture was poured intolN HCl and extracted with additional methylene chloride. The organiclayer was washed with saturated NaHCO₃ solution, dried with MgSO₄ andthe solvent evaporated to yield a yellow foam: 1.6 g., 86%. Thestructure is consistent with nuclear magnetic resonance, infrared andmass spectral data.

The following is a table of certain selected compounds that arepreparable according to the procedure described herein. Compound numbersare assigned to each compound and are used throughout the remainder ofthe application.

                                      TABLE I                                     __________________________________________________________________________     ##STR8##                                                                     Cmpd.                                                                         No. R  R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                          R.sup.4                                                                         R.sup.5                                                                          R.sup.6                                                                          R.sup.7                                                                              R.sup.8 R.sup.9                                                                          R.sup.10                            __________________________________________________________________________    1.  NO.sub. 2                                                                        CH.sub.3                                                                         CH.sub.3                                                                         H  H H  H  H      4-SO.sub.2 CH.sub.3                                                                   CH.sub.3                                                                         CH.sub.2 CH.sub.2                   2.  NO.sub.2                                                                         H  H  H  H H  H  H      4-CF.sub.3                                                                            CH.sub.3                                                                         CH.sub.2 CHCHCH.sub.2               3.  Cl H  H  CH.sub.3                                                                         H H  H  3-OCH.sub.2 CH.sub.3                                                                 4-SO.sub.2 CH.sub.2 CH.sub.3                                                          CH.sub.3                                                                         CH.sub.2 CH.sub.2                   4..sup.a)                                                                         Cl H  H  H  H H  H  H      4-SO.sub.2 CH.sub.3                                                                   CH.sub.3                                                                         CH.sub.2 CH.sub.3                   5.  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H H  H  H      H       CH.sub.3                                                                         CH.sub.2 CH.sub.2                   6.  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H H  H  H      4-SO.sub.2 CH.sub.3                                                                   CH.sub.3                                                                         CH.sub.2 CH.sub.2 CH.sub.2                                                    CH.sub.2                            7.  NO.sub.2                                                                         CH.sub.3                                                                         CH.sub.3                                                                         O    CH.sub.3                                                                         CH.sub.3                                                                         H      4-CF.sub.3                                                                            CH.sub.3                                                                         CH.sub.2 CH.sub.3                   __________________________________________________________________________     .sup.a) Prepared in Example II.                                          

Herbicidal Screening Tests

As previously mentioned, the herein described compounds produced in theabove-described manner are phytotoxic compounds which are useful andvaluable in controlling various plant species. Selected compounds ofthis invention were tested as herbicides in the following manner.

Pre-emergence Multi-weed Herbicide Test: On the day preceding treatment,seeds of eight different weed species are planted in loamy sand soil inindividual rows using one species per row across the width of a flat.The weeds used are green foxtail (FT) (Setaria viridis), giant foxtail(GFT) (Sentenia faberi), watergrass (WG) (Echinochloa crusgalli),broadleaf signalgrass (BSG) (Brachiaria platyphylla), annualmorning-glory (AMG) (Ipomoea lacunosa), cocklebur (CB) (Xanthium sp.),velvetleaf (VL) (Abutilon theophrasti), and yellow nutsedge (YNS)(Cyperus esculentus). Ample seeds are planted to give about 20 to 40seedlings per row, after emergence, depending upon the size of theplants.

Using an analytical balance, 25 milligrams (mg) of the compound to betested are weighed out on a piece of glassine weighing paper. The paperand compound are placed in a 60 milliliter (ml) wide-mouth clear bottleand dissolved in a solution of 20 ml of acetone and 20 ml watercontaining enough polyoxyethylene sorbitan monolaurate emulsifier togive a final solution of 0.5% (v/v). The solution is then sprayed on aseeded flat on a linear spray table calibrated to deliver 400 L/ha. Theapplication rate was 0.25 kg/ha.

After treatment, the flats are placed in the greenhouse at a temperatureof 70° to 80° F. and watered by sprinkling. Two weeks after treatment,the degree of injury or control is determined by comparison withuntreated check plants of the same age. The injury rating from 0 to 100%is recorded for each species as percent control with 0% representing noinjury and 100% representing complete control.

Several compounds were evaluated at an application rate of 0.17 kg/hafor pre- and post-emergence activity against the same weed species thatare used in the above-described pre-emergent multi-herbicide test.

The process was generally similar to the pre-emergence herbicide testprocedure described above except that only 17 milligrams of testcompound were weighted out.

The results of the 0.25 kg/ha pre-emergence test are shown in Table II.The results of the 0.17 kg/ha pre-emergence test are shown in thefollowing Table IV.

                  TABLE II                                                        ______________________________________                                        Pre-emergence Herbicidal Activity                                             Application Rate - 0.25 kg/ha                                                 Compd.                                                                        No.     GFT    FT     WG   BSG  AMG   CB   VL   YNS                           ______________________________________                                        1       100    --     100  100  100   100  100  98                            2        50     0      0    10   0     0    80   0                            5        30    40     --    85   5     20  100  50                            ______________________________________                                         (--) = Not tested.                                                       

Post-emergence Multi-weed Herbicide Test: This test is conducted in anidentical manner to the testing procedure for the pre-emergencemulti-weed herbicide test, except the seeds of the eight different weedspecies are planted 10-12 days before treatment. Also, watering of thetreated flats is confined to the soil surface and not to the foliage ofthe sprouted plants.

The results of the post-emergence multi-weed herbicide test are reportedin Tables III and V.

                  TABLE III                                                       ______________________________________                                        Post-emergence Multi-weed Herbicidal Activity                                 Application Rate - 0.25 kg/ha                                                 Compd.                                                                        No.     GFT    FT     WG   BSG  AMG   CB   VL   YNS                           ______________________________________                                        1       80     --     100  95   100   90   100  70                            2        0      0      60   5    5    10    85   0                            5       15     60      85  60    85   95    85  50                            ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                        Pre-emergence Herbicidal Activity                                             Application Rate - 0.17 kg/ha                                                 Compd.                                                                        No.     GTF    FT     WG   BSG  AMG   CB   VL   YNS                           ______________________________________                                        3       100    100    100  100  70     90  100  98                            4        50     90    100   50  60    100  100  98                            ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        Post-emergence Herbicidal Activity                                            Application Rate - 0.17 kg/ha                                                 Compd.                                                                        No.     GTF    FT     WG   BSG  AMG   CB   VL   YNS                           ______________________________________                                        3       100    100    100  100   70   --   100  50                            4        20     20     95  100  100   --   100  30                            ______________________________________                                         (--) = Not tested.                                                       

The compounds of the present invention are useful as herbicides and canbe applied in a variety of ways at various concentrations. In practice,the compounds herein defined are formulated into herbicidalcompositions, by admixture, in herbicidally effective amounts, with theadjuvants and carriers normally employed for facilitating the dispersionof active ingredients for agricultural applications, recognizing thefact that the formulation and mode of application of a toxicant mayaffect the activity of the materials in a given application. Thus, theseactive herbicidal compounds may be formulated as granules of relativelylarge particle size, as wettable powders, as emulsifiable concentrates,as powdery dusts, as solutions or as any of several other known types offormulations, depending upon the desired mode of application. Preferredformulations for pre-emergence herbicidal applications are wettablepowders, emulsifiable concentrates and granules. These formulations maycontain as little as about 0.5% to as much as about 95% or more byweight of active ingredient. A herbicidally effective amount dependsupon the nature of the seeds or plants to be controlled and the rate ofapplication varies from about 0.05 to approximately 10 pounds per acre,preferably from about 0.1 to about 4 pounds per acre.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other dispersants. The wettable powder isultimately applied to the soil either as a dry dust or as a dispersionin water or other liquid. Typical carriers for wettable powders includefuller's earth, kaolin clays, silicas and other readily wet organic orinorganic diluents. Wettable powders normally are prepared to containabout 5% to about 95% of the active ingredient and usually also containa small amount of wetting, dispersing, or emulsifying agent tofacilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which aredispersible in water or other dispersant, and may consist entirely ofthe active compound with a liquid or solid emulsifying agent, or mayalso contain a liquid carrier, such as xylene, heavy aromatic naphthal,isophorone and other non-volatile organic solvents. For herbicidalapplication, these concentrates are dispersed in water or other liquidcarrier and normally applied as a spray to the area to be treated. Thepercentage by weight of the essential active ingredient may varyaccording to the manner in which the composition is to be applied, butin general comprises about 0.5% to 95% of active ingredient by weight ofthe herbicidal composition.

Granular formulations wherein the toxicant is carried on relativelycoarse particles, are usually applied without dilution to the area inwhich suppression of vegetation is desired. Typical carriers forgranular formulations include sand, fuller's earth, bentonite clays,vermiculite, perlite and other organic or inorganic materials whichabsorb or which may be coated with the toxicant. Granular formulationsnormally are prepared to contain about 5% to about 25% of activeingredients which may include surface-active agents such heavy aromaticnaphthas, kerosene or other petroleum fractions, or vegetable oils;and/or stickers such as dextrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents used in agriculturalformulations include, for example, the alkyl and alkylaryl sulfonatesand sulfates and their sodium salts; polyhydric alcohols; and othertypes of surface-active agents, many of which are available in commerce.The surface-active agent, when used, normally comprises from 0.1% to 15%by weight of the herbicidal compositions.

Dusts, which are free-flowing admixtures of the active ingredient withfinely divided solids such as talc, clays, flours and other organic andinorganic solids which act as dispersants and carriers for the toxicant,are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solidtoxicant in a liquid carrier such as water or oil, are employed forspecific purposes. These formulations normally contain about 5% to about95% of active ingredient by weight, and may also contain small amountsof a wetting, dispersing or emulsifying agent to facilitate dispersion.For application, the pastes are normally diluted and applied as a sprayto the area to be affected.

Other useful formulations for herbicidal applications include simplesolutions of the active ingredient in a dispersant in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene and other organic solvents. Pressurizedsprays, typically aerosols, wherein the active ingredient is dispersedin finely-divided form as a result of vaporization of a low boilingdispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention are applied to the plantsin the conventional manner. Thus, the dust and liquid compositions canbe applied to the plant by the use of power-dusters, boom and handsprayers and spray dusters. The compositions can also be applied fromairplanes as a dust or a spray because they are effective in very lowdosages. In order to modify or control growth of germinating seeds oremerging seedlings, as a typical example, the dust and liquidcompositions are applied to the soil according to conventional methodsand are distributed in the soil to a depth of at least 1/2 inch belowthe soil surface. It is not necessary that the phytotoxic compositionsbe admixed with the soil particles since these compositions can also beapplied merely by spraying or sprinkling the surface of the soil. Thephytotoxic compositions of this invention can also be applied byaddition to irrigation water supplied to the field to be treated. Thismethod of application permits the penetration of the compositions intothe soil as the water is absorbed therein. Dust compositions, granularcompositions or liquid formulations applied to the surface of the soilcan be distributed below the surface of the soil by conventional meanssuch as discing, dragging or mixing operations.

    ______________________________________                                        EMULSIFIABLE CONCENTRATE FORMULATIONS                                         General Formula with Ranges                                                                    Specific Formula                                             ______________________________________                                        herbicidal compound                                                                         5-55   herbicidal compound                                                                           54                                       surfactant(s)                                                                               5-25   proprietary blend of oil-                                                                     10                                       solvent(s)   20-90   soluble sulfonates and                                                100%    polyoxyethylene ethers                                                        polar solvent   27                                                            petroleum hydrocarbon                                                                          9                                                                             100%                                    ______________________________________                                    

    ______________________________________                                        WETTABLE POWDER FORMULATIONS                                                  ______________________________________                                        herbicidal compound                                                                         3-90   herbicidal compound                                                                          80                                        wetting agent                                                                              0.5-2   sodium dialkyl 0.5                                       dispersing agent                                                                           1-8     naphthalene sulfonate                                    diluent(s)   8.5-87  sodium lignosulfonate                                                                        7                                                      100%    attapulgite clay                                                                             12.5                                                                          100%                                      ______________________________________                                    

    ______________________________________                                        EXTRUDED GRANULAR FORMULATIONS                                                ______________________________________                                        herbicidal compound                                                                         1-20   herbicidal compound                                                                          10                                        binding agent                                                                               0-10   lignin sulfonate                                                                              5                                        diluent(s)   70-99   calcium carbonate                                                                            85                                                     100%                    100%                                     ______________________________________                                    

    ______________________________________                                        FLOWABLE FORMULATIONS                                                         ______________________________________                                        herbicidal compound                                                                        20-70     herbicidal    45                                       surfactant(s)                                                                               1-10     compound                                               suspending agent(s)                                                                        0.05-1    polyoxyethylene                                                                             5                                        antifreeze agent                                                                            1-10     ether                                                  antimicrobial agent                                                                         1-10     attagel       0.05                                     antifoam agent                                                                             0.1-1     propylene glycol                                                                            10                                       solvent       7.95-76.85                                                                             BIT           0.03                                                  100%      silicone defoamer                                                                           0.02                                                            water         39.9                                                                          100%                                     ______________________________________                                    

The phytotoxic compositions of this invention can also contain otheradditives, for example, fertilizers, other herbicides and otherpesticides, used as adjuvant or in combination with any of theabove-described adjuvants. Fertilizers useful in combination with theactive ingredients include, for example, ammonium nitrate, urea andsuperphosphate.

The herbicidal compounds of this invention can be used in combinationwith other herbicidal compounds for broader spectrum control ofundesirable vegetation. Examples of other herbicidal compounds are asfollows:

1. Anilides

Alachlor--2-chloro-2', 6'-diethyl-N-(methoxymethyl)acetanilide

Metolachlor--2-chloro-2'-methyl-6'ethyl-N-methoxy-isopropyl-2-acetanilide

Propanil--N-(3,4-dichlorophenyl)propionanilide

Acetachlor--2-chloro-2'-methyl-6'ethyl-N-ethoxymethylacetanilide

2. Triazines

Atrazine--2-chloro-4-(ethylamino)-6-isopropylamino)-s-triazine

Cyanazine--2-chloro-4-(1-cyano-1-methylethylamino)-6-ethylamino-s-triazine

Metribuzin--4-amino-6-tert-butyl-3-(methylthio) -1,2,4-triazin-5(4H)-one

3. Thiocarbamates

Molinate--S-ethyl hexahydro-lH-azepine-1-carbothioate

Butylate--S-ethyl diisobutylthiocarbamate

4. Ureas

Monuron--3-(p-chlorophenyl)-1,1-dimethylurea

Linuron--3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea

5. Toluidines

Trifluralin--α,α,α-trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine

Pendimethalin--N-(1-ethylpropyl)-3,4-dimethyl-2, 6-dinitrobenzeneamine

6. Hormones

2,4-D--(2,4-dichlorophnoexy) acetic acid

MCPA--(2-methyl-4-chlorophenoxy) acetic acid

7. Diazines

Bentazon--3-isopropyl-lH-2,3,1-benzothiadiazin-4(3H)-one 2,2-dioxide

Oxadiazon--2-tert-butyl-4-(2,4-dichloro-5-isopropoxyphenyl)-Δ²-1,3,4-oxadiazolin-5-one

8. Diphenyl ethers

Acifluorfen--sodium5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate

Fluazifop--butyl -(±)-butyl2-[4[(5-(trifluoromethyl)-2-pyridinyl)oxy]phenoxy]propanoatepyridinyl)oxy]phenoxy]propanoate

Chlomethoxynil--2,4-dichlorophenyl 3-methoxy-4-nitrophenyl ether

9. Imidazolinones

Imazaquin--2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinolincarboxylic acid

10. Sulfonyl ureas

Bensulfuron methyl--methyl 2-[[[[[(4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]amino]sulfonyl]methyl]benzoate

Chlorimuron ethyl--ethyl2-(((((4-chloro-6-methoxypyrimidin-2-yl)amino)carbonyl)amino)sulfonyl)benzoate

11. 2-(2-Substituted benzoyl)-1,3-cyclohexanediones

2- (2'-chloro-4-methysulfonyl benzoyl)-1, 3-cyclohexanedione

12. Miscellaneous compounds

Dimethazone--2-(2-chlorophenyl)methyl-4, 4-dimethyl-3-isoxazolidinone

Norflurazon--4-chloro-5-(methylamino)-2-α,α,α-trifluoro-m-tolyl)-3-(2H)-pyridazinone

Dalapon--2,2-dichloropropionic acid

Glyphosate--isopropyl amine salt of N-(phosphonomethyl) glycine

Fenoxaprop-ethyl--(+)-ethyl-2,4-((6-chloro-2-benzoxazolyloxy)phenoxy)propanoate

What is claimed is:
 1. A compound of the formula ##STR9## wherein R ishalogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro; cyano; C₁ -C₂ haloalkyl, orR^(a) SO_(n) --wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl;R¹ ishydrogen or C₁ -C₄ alkyl; R² is hydrogen or C₁ -C₂ alkyl; or R¹ and R²together are alkylene having 2 to 5 carbon atoms; R³ is hydrogen or C₁-C₄ alkyl; R⁴ is hydrogen or C₁ -C₄ alkyl; or R³ and R⁴ together areoxo; R⁵ is hydrogen or C₁ -C₄ alkyl; R⁶ is hydrogen or C₁ -C₄ alkyl; orR⁵ and R⁶ together are alkylene having 2 to 5 carbon atoms; R⁷ and R⁸independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁-C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄haloalkyl; (9) R^(b) SO_(n) --wherein n is the integer 0, 1 or 2; andR^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen orcyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) andR^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e)C(O)--wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) SO₂ NR^(c)R^(d) wherein R^(c) and R^(d) are as defined; (13) --N(R^(c))C(O)R^(d)wherein R^(c) and R^(d) are as defined; or (14) --CH₂ CH₂ OCH₃ or --CH₂CH₂ OC₂ H₅ ; with the proviso that R⁷ is not at the 6-position; and R⁹is hydrogen or C₁ -C₄ alkyl; and R¹⁰ is C₂ -C₆ alkylene, C₄ -C₈alkenylene or C₄ -C₈ alkynylene with the proviso that R⁷ is not at the6-position.
 2. The compounds of claim 1 wherein R is chlorine, bromine,C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro, C₁ -C₂ alkylthio or C₁ -C₂alkylsulfonyl; R¹ is hydrogen or methyl; R² is hydrogen or methyl; R³ ishydrogen or methyl; R⁴ is hydrogen or methyl; R⁵ is hydrogen or methyl;R⁶ is hydrogen or methyl; R⁷ and R⁸ independently are (1) hydrogen; (2)halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6)cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) --wherein n isthe integer 0, or 2; and R^(b) is (a) C₁ -C₂ alkyl; or (b) C₁ -C₂ alkylsubstituted with halogen or (10) --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ ;and R⁹ is hydrogen or methyl and R¹⁰ is C₂ -C₄ alkylene.
 3. The compoundof claim 2 wherein R⁷ is hydrogen, methylthio, methoxy, ethoxy, --CH₂CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ and is in the 3-position, and R⁸ ishydrogen, chlorine, bromine, fluorine, trifluoromethyl or R^(b) SO_(n)wherein R^(b) is C₁ -C₃ alkyl and n is the integer 0 or
 2. 4. Thecompound of claim 2 wherein R is chlorine; R¹ is hydrogen; R² ishydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ ishydrogen; R⁷ is hydrogen; R⁸ is 4-methylsulfonyl; R⁹ is methyl; and R¹⁰is ethylene.
 5. The compound of claim 2 wherein R is nitro; R¹ ismethyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶is hydrogen; R⁷ is hydrogen; R⁸ is hydrogen; R⁹ is methyl; and R¹⁰ isethylene.
 6. The compound of claim 2 wherein R is chlorine; R¹ ishydrogen; R² is hydrogen; R³ is methyl; R⁴ is hydrogen; R⁵ is hydrogen;R⁶ is hydrogen; R⁷ is 3-ethoxy; R⁸ is 4--CH₃ SO₂ --; and R⁹ is methyland R¹⁰ is ethylene.
 7. The compound of claim 2 wherein R is nitro; R¹is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen;R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is hydrogen; R⁹ is methyl; and R¹⁰ isethylene.
 8. The compound of claim 2 wherein R is nitro; R¹ is methyl;R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ ishydrogen; R⁷ is hydrogen; R⁸ is 4-trifluoromethyl; R⁹ is methyl; and R¹⁰is --CH₂ --CH═CH--CH₂ --.
 9. The compound of claim 2 wherein R is nitro;R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ ishydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ --; R⁹ ismethyl and R¹⁰ is butylene.
 10. The compound of claim 1 wherein R isnitro; R¹ is methyl; R² is methyl; R³ and R⁴ are oxo; R⁵ is methyl; R⁶is methyl; R⁷ is hydrogen; R⁸ is 4-trifluoromethyl; R⁹ is methyl; andR¹⁰ is ethylene.
 11. The method of controlling undesirable vegetationcomprising applying to the area where control is desired, anherbicidally effective amount of a compound having the formula ##STR10##wherein R is halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro; cyano; C₁ -C₂haloalkyl, or R^(a) SO_(n) --wherein n is 0 or 2 and R^(a) is C₁ -C₂alkyl;R¹ is hydrogen or C₁ -C₄ alkyl; R² is hydrogen or C₁ -C₄ alkyl; orR¹ and R² together are alkylene having 2 to 5 carbon atoms; R³ ishydrogen or C₁ -C₄ alkyl; R⁴ is hydrogen or C₁ -C₄ alkyl; or R³ and R⁴together are oxo; R⁵ is hydrogen or C₁ -C₄ alkyl; R⁶ is hydrogen or C₁-C₄ alkyl; or R⁵ and R⁶ together are alkylene having 2 to 5 carbonatoms; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro;(8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) --wherein n is the integer 0, 1or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted withhalogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) whereinR^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e)C(O)--wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) SO₂ NR^(c)R^(d) wherein R^(c) and R^(d) are as defined; (13) --N(R^(c))C(O)R^(d)wherein R^(c) and R^(d) are as defined; or (14) --CH₂ CH₂ OCH₃ or --CH₂CH₂ OC₂ H₅ ; with the proviso that R⁷ is not at the 6-position; and R⁹is hydrogen or C₁ -C₄ alkyl; and R¹⁰ is C₂ -C₆ alkylene, C₄ -C₈alkenylene or C₄ -C₈ alkenylene
 12. The method of claim 11 wherein R ischlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro, C₁ -C₂ alkylthioor C₁ -C₂ alkylsulfonyl; R¹ is hydrogen or methyl; R² is hydrogen ormethyl; R³ is hydrogen or methyl; R⁴ is hydrogen or methyl; R⁵ ishydrogen or methyl; R⁶ is hydrogen or methyl; R⁷ and R⁸ independentlyare (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5)trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b)SO_(n) --wherein n is the integer 0 or 2; and R^(b) is (a) C₁ -C₂ alkyl;or (b) C₁ -C₂ alkyl substituted with halogen or (10) --CH₂ CH₂ OCH₃ or--CH₂ CH₂ OC₂ H₅ ; and R⁹ is hydrogen or methyl and R¹⁰ is C₂ -C₄alkylene.
 13. The method of claim 11 wherein R is chlorine; R¹ ishydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ ishydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is 4-methylsulfonyl; R⁹ ismethyl; and R¹⁰ is ethylene.
 14. The method of claim 12 wherein R ischlorine; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ ishydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is4-methylsulfonyl; R⁹ is methyl; and R¹⁰ is ethylene.
 15. The method ofclaim 12 wherein R is nitro; R¹ is methyl; R² is methyl; R³ is hydrogen;R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ ishydrogen; R⁹ is methyl; and R¹⁰ is ethylene.
 16. The method of claim 12wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is methyl; R⁴is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is 3-ethyloxy; R⁸ is4--CH₃ CH₂ SO₂ --; R⁹ is methyl and R¹⁰ is ethylene.
 17. The method ofclaim 12 wherein R is nitro; R¹ is methyl; R² is methyl; R³ is hydrogen;R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is4--CH₃ SO₂ --; R⁹ is methyl; and R¹⁰ is ethylene.
 18. The method ofclaim 12 wherein R is nitro; R¹ is hydrogen; R² is hydrogen; R³ ishydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ ishydrogen; R⁸ is 4-trifluoromethyl; R⁹ is methyl; and R¹⁰ is2-butenethylene.
 19. The method of claim 12 wherein R is nitro; R¹ ismethyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶is hydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ --; R⁹ is methyl and R¹⁰is butylene.
 20. The method of claim 11 wherein R is nitro; R¹ ismethyl; R² is methyl; R³ and R⁴ are oxo; R⁵ is methyl; R⁶ is methyl; R⁷is hydrogen; R⁸ is 4-trifluoromethyl; R⁹ is methyl and R¹⁰ is ethylene.21. An herbicidal composition comprising an herbicidally activebis(2-benzoyl-3-oxo-cyclohexenyl)diamine.
 22. An herbicidal compositioncomprising an herbicidally active compound having the structural formula##STR11## wherein R is halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro;cyano; C₁ -C₂ haloalkyl, or R^(a) SO_(n) --wherein n is 0 or 2 and R^(a)is C₁ -C₂ alkyl;R¹ is hydrogen or C₁ -C₄ alkyl; R² is hydrogen or C₁ -C₂alkyl; or R¹ and R² together are alkylene having 2 to 5 carbon atoms; R³is hydrogen or C₁ -C₄ alkyl; R⁴ is hydrogen or C₁ -C₄ alkyl; or R³ andR⁴ together are oxo; R⁵ is hydrogen or C₁ -C₄ alkyl; R⁶ is hydrogen orC₁ -C₄ alkyl; or R⁵ and R⁶ together are alkylene having 2 to 5 carbonatoms; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro;(8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) --wherein n is the integer 0, 1or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted withhalogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) whereinR^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e)C(O)--wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) SO₂ NR^(c)R^(d) wherein R^(c) and R^(d) are as defined; (13) --N(R^(c))C(O)R^(d)wherein R^(c) and R^(d) are as defined; or (14) --CH₂ CH₂ OCH₃ or --CH₂CH₂ OC₂ H₅ ; with the proviso that R⁷ is not at the 6-position; and R⁹is hydrogen or C₁ -C₄ alkyl; and R¹⁰ is C₂ -C₆ alkylene, C₄ -C₈alkenylene or C₄ -C₈ alkynylene and an inert carrier therefor.
 23. Thecomposition of claim 22 wherein R is chlorine, bromine, C₁ -C₂ alkyl, C₁-C₂ alkoxy, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; R¹ ishydrogen or methyl; R² is hydrogen or methyl; R³ is hydrogen or methyl;R⁴ is hydrogen or methyl; R⁵ is hydrogen or methyl; R⁶ is hydrogen ormethyl; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁-C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7)nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) --wherein n is the integer0 or 2; and R^(b) is (a) C₁ -C₂ alkyl; or (b) C₁ -C₂ alkyl substitutedwith halogen or (10) --CH₂ CH₂ OCH₃ or --CH₂ CH₂ OC₂ H₅ ; and R⁹ ishydrogen or methyl and R¹⁰ is C₂ -C₄ alkylene.
 24. The composition ofclaim 23 wherein R⁷ is hydrogen, methylthio, methoxy, ethoxy, --CH₂ CH₂OCH₃ or --CH₂ CH₂ OC₂ H₅ and is in the 3-position, and R⁸ is hydrogen,chlorine, bromine, fluorine, trifluoromethyl or R^(b) SO_(n) whereinR^(b) is C₁ -C₃ alkyl and n is the integer 0 or
 2. 25. The compositionof claim 23 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ ishydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ ishydrogen; R⁸ is 4-methylsulfonyl; R⁹ is methyl; and R¹⁰ is ethylene. 26.The composition of claim 23 wherein R is nitro; R¹ is methyl; R² ismethyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen;R⁷ is hydrogen; R⁸ is hydrogen; R⁹ is methyl; and R¹⁰ is ethylene. 27.The composition of claim 23 wherein R is chlorine; R¹ is hydrogen; R² ishydrogen; R³ is methyl; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen;R⁷ is 3-ethoxy; R⁸ is 4--CH₃ SO₂ --; and R⁹ is methyl and R¹⁰ isethylene.
 28. The composition of claim 23 wherein R is nitro; R¹ ismethyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶is hydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ --; R⁹ is methyl; and R¹⁰is ethylene.
 29. The composition of claim 23 wherein R is nitro; R¹ ismethyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶is hydrogen; R⁷ is hydrogen; R⁸ is 4-trifluoromethyl; R⁹ is methyl; andR¹⁰ is --CH₂ --CH═CH--CH₂ --.
 30. The composition of claim 23 wherein Ris nitro; R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ --; R⁹ ismethyl and R¹⁰ is butylene.
 31. The composition of claim 22 wherein R isnitro; R¹ is methyl; R² is methyl; R³ and R⁴ are oxo; R⁵ is methyl; R⁶is methyl; R⁷ is hydrogen; R⁸ is 4-trifluoromethyl; R⁹ is methyl; andR¹⁰ is ethylene.